Zeolite-substrate composite comprising a patterned zeolite layer on a substrate and preparation thereof

ABSTRACT

The present invention relates to a method for the preparation of a zeolite-substrate composite comprising a patterned zeolite monolayer or multilayer on a substrate, which comprises forming a pattern of a linking compound on the substrate by a selective irradiation with a UV ray, a selective application of a linking compound or a blocking compound, or a selective deposition of a metal, and combining zeolite particles on the portion whereon the linking compound is patterned. The substrate is selected from a group consisting of a substrate having surface hydroxyl groups, a metal capable of being reacted with thiol or amino groups, and a polymeric material having various surface functional groups. The present invention also relates to a zeolite-substrate composite comprising a patterned zeolite monolayer or multilayer on a substrate prepared by said method.

TECHNICAL FIELD

[0001] The present invention relates to a zeolite-substrate compositecomprising a patterned zeolite layer and a method of preparation of thesame. More specifically, the present invention relates to a method forthe preparation of a zeolite-substrate composite comprising a patternedzeolite monolayer or multilayer on a substrate, which comprises forminga pattern of a linking compound on the substrate by binding a linkingcompound on the substrate surface followed by a selective irradiationwith UV ray thereon, or by a selective coating on a portion of thesubstrate surface with a linking compound or a blocking compound such asoctadecyltrichlorosilane, or by a selective deposition of a metal suchas platinum on the substrate surface followed by binding a linkingcompound thereon, and combining selectively zeolite or zeotype molecularsieve (hereinafter, referred as to “zeolite” or “molecular sieve”) alongwith said pattern, wherein said substrate is selected from a groupconsisting of a substance having surface hydroxyl groups, a metalcapable of being reacted with thiol group (—SH) or amino group (—NH₂)and a polymeric material having various surface functional groups. Thepresent invention also relates to the zeolite-substrate compositeprepared thereby.

BACKGROUND ART

[0002] Molecular sieves including zeolite are important materials, whichhave been employed widely in the household item level and the industrialfield. Zeolite generally presents in the form of fine powder, whichgives both advantages and disadvantages for using zeolite. Combiningthose zeolite particles firmly with various substrates through chemicalbond, a wide industrial applicability of zeolite can be expected.

[0003] Further, it can be said that it is significant to adjust thezeolite so as to have a uniform orientation to the substrate as it caninduce new physical properties expectedly. Still further, if zeoliteparticles are combined to the substrate surface so as to have aselective and/or uniform orientation, novel characteristics that havenever been found in the conventional material would be expected and anepoch-making development may be achieved.

[0004] “Zeolite” is a generic name of crystalline aluminosilicate, whichconstitutes the pore skeleton of zeolite molecules and bears an anioniccharge for each aluminum atom. Cations for offsetting such anion chargesare present within the pore space and the remaining pore space is filledwith water. The three dimensional pore structure of the zeolite moleculevaries depending on the shape and size of the pore, and the porediameter is usually determined by size of the molecule. Therefore, basedon the shape and size of the pore, zeolite has a shape selectivity for amolecule entering into the pore. In this connection, zeolite is calledas a molecular sieve.

[0005] Zeolite (or molecular sieve) or analogous molecular sieves(hereinafter, referred to as zeolite or its analogs) show diversechemical and physical properties depending on its chemical composition,structure, pre-treatment method, etc. Especially, modified zeolite inwhich protons are replaced with other cations is widely used as acracking catalyst of crude oil in the petrochemical industry, thanks toits resistance to high temperature. Further, zeolite is widely used as awater-absorbing drying agent, adsorbent, gas-purifying agent, ionexchanger, additives for detergent, soil improving agent or the like. Anextensive study is now being made on its application as a sensorcarrier.

[0006] Meanwhile, there are known many other zeolite-like molecularsieves (or zeotype molecular sieves) wherein a part or all of silicon(Si) and/or aluminum (Al) atoms constituting the structural skeleton ofzeolite molecule are replaced with other elements. For example, amesoporous silica (MCM-series mesoporous silica and silicalite, etc.) inwhich aluminum atoms are completely eliminated, an alpo(AlPO₄)-typemolecular sieve in which silicon atoms are replaced with phosporousatoms, and other molecular sieve or its analog wherein skeleton metalatoms are partly replaced with various metal atom such as Ti, Mn, Co,Fe, Zn, etc., have been developed and widely used.

[0007] For better utilization of zeolite or its analogs, studies havebeen carried out to develop methods of attaching zeolite particles tothe surface of substrates such as glass, ceramics, polymeric materials,metal, etc. [L. C. Boudreau, J. A. Kuck, M. Tsapatsis, J Membr. Sci.1999, 152, 41-59; Z. Li, C. Lai, T. E. Mallouk, Inorg. Chem. 1989, 28,178-182; L. C. Boudreau, J. A. Kuck, M. Tsapatsis, J. Membr. Sci. 1999,152, 41-59; J. C. Jansen, D. Kashchiev, A. Erdem-Senataler, Stud. Surf,Sci. Catal, 1994, 85. 215-250; R. Althoff, K. Unger, F. Shuff,Microporous Mater, 1994, 2, 557-562].

[0008] However it is not easy to perfectly control the thickness andorientation of a zeolite monolayer through conventional methods. Theinventors have developed a simple and economic method for thepreparation of a composite of substrate-linking compound-zeolite bychemically changing the surface of the substrate or zeolite by using alinking compound having functional groups capable of reacting with thesubstrate or zeolite, respectively. [See: PCT/KR00/01001 with claiming apriority based on Korean Patent Application No. 2000-19667 (filed onApr. 14, 2000)].

[0009] On the other hand, numerous studies have been carried out inrespect of the formation of the pattern on the surface of substratessuch as glass, ceramics, polymeric materials and metal. As toconventionally known methods for forming a pattern, the following threemethods can be exemplified basically.

[0010] The first method is a selective irradiation wherein UV ray isirradiated with a photomask to selectively form a pattern. The secondmethod is a stamping method wherein a pattern is previously preparedonto a cast by using polydimethylsiloxane (PDMS), a linking compound ora blocking compound such as octadecyltrichlorosilane is applied onto thecast, and said cast is stamped onto the substrate to form said patternon the substrate. The third method is a selective metal depositionwherein a metal grid is stuck to a substrate and a deposited layer of ametal such as platinum is selectively formed on the substrate to form apattern.

[0011] As set forth herein above, such technology wherein a surface ismodified by forming a pattern on a substrate so that the chemicalreactivity of the surface of the substrate varies along the patternformed on said substrate is well known. There are many technicaldifficulties in modifying the surface of zeolite so as to have achemical reactivity to combine the zeolite particles chemically onto asubstrate.

[0012] The inventors have already achieved a great development of thechemical procedure by modifying a chemical reaction that happens in asolution state so that it can happen at the surface of a material.Further, the inventors have extensively studied in order to producevarious composites by utilizing the methods thus developed.

[0013] As a result, the inventors have developed a method for theformation of a patterned monolayer or multilayer of zeolite having anexcellent durability and orientation, which comprises forming a patternon the substrate by means of UV ray, a blocking compound, a metal (e.g.,platinum) deposition, etc. and chemically combining of zeolite onto thepatterned surface of the substrate.

[0014] As set forth hereinabove, it has been well known to modify thesurface so as to the different chemical reactivity along the pattern byforming a pattern thereon by means of UV ray, a linking or blockingcompound (e.g., octadecyltrichlorosilane), a metal (e.g., platinum)deposition, etc. However, it has never been reported to form a patternedzeolite layer on surface-modified substrate.

[0015] It is now found that, when the method described in said KoreanPatent Application No.2000-19667 filed by the inventors, i.e., when themethod of combining zeolite to a substrate via a chemical bonding isemployed, it is possible to laminate on a substrate on which a patternhas been formed a zeolite layer along the pattern formed on thesubstrate, to laminate not only a monolayer but also a multilayer, andto easily and diversely control the shape and material (zeolite type) ineach layer.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention relates to a method for the preparation ofa zeolite-substrate composite, namely a composite of substrate-linkingcompound-zeolite comprising a patterned zeolite monolayer or multilayer,which comprises forming a pattern of a linking compound on the substrateby binding a linking compound on the substrate surface followed by aselective irradiation with UV ray thereon, or by a selective coating ona portion of the substrate surface with a linking compound or a blockingcompound such as octadecyltrichlorosilane, or by a selective depositionof a metal such as platinum on the substrate surface followed by bindinga linking compound thereon, and combining selectively zeolite along withsaid pattern, wherein said substrate is selected from a group consistingof a substance having surface hydroxyl groups, a metal capable of beingreacted with thiol group (—SH) or amino group (—NH₂) and a polymericmaterial having various surface functional groups.

[0017] Accordingly, the first object of the present invention is toprovide a method for the preparation of a zeolite-substrate composite,namely a composite of substrate-linking compound-zeolite comprising apatterned zeolite monolayer or multilayer, characterized in that itcomprises (i) combining a linking compound onto the surface ofsubstrate, (ii) modifying the linking compound combined to the substrateor the functional group thereof by irradiating UV ray through aphotomask having a pattern, (iii) selectively forming a zeolite layer onthe area to which UV ray is irradiated or the area to which UV ray isnot irradiate, and (iv) optionally performing a calcination.

[0018] In the above method of the first object, after removing theportion to which UV ray is irradiated of the portion to which UV ray isnot irradiated, a zeolite layer may be formed.

[0019] The second object of the present invention is to provide a methodfor the preparation of a zeolite-substrate composite, namely a compositeof substrate-linking compound-zeolite comprising a patterned zeolitemonolayer or multilayer, characterized in that it comprises (i)combining a linking compound to a part of the surface of the substrateso as to have a predetermined pattern and then combining a blockingcompound to the remaining surface of the substrate, or combining ablocking compound to a part of the surface of the substrate so as tohave a predetermined pattern and then combining a linking compound tothe remaining surface of the substrate, (ii) forming a zeolite layer onthe area to which the linking compound is combined, and (iii) optionallyperforming a calcination.

[0020] In the above method of the second object, the linking compound orblocking compound can be coated on a part of the substrate surface bythe stamping method.

[0021] The third object of the present invention is to provide a methodfor the preparation of a zeolite-substrate composite, namely a compositeof substrate-linking compound-zeolite comprising a patterned zeolitemonolayer or multilayer, characterized in that it comprises (i)depositing a metal such as platinum onto a part of the substrate surfaceto form a metal layer so as to have a predetermined pattern. (ii)forming a zeolite layer by growing crystal or combining zeolite-linkingcompound on the remaining area, and (iii) optionally performing acalcination.

[0022] The fourth object of the present invention is to provide apatterned monolayer or multilayer of zeolite prepared by said method,wherein the type and kind of zeolite as well as the pattern style ineach of the layer can be identical with or different from each otherrespectively.

[0023] In the present invention, it is possible to repeat each of thefirst, second and third methods or combination thereof in order toproduce a composite of patterned zeolite multilayer.

[0024] The present invention will be illustrated in detail below.

[0025] In the present invention, the term of “zeolite” or “molecularsieve” has a meaning including zeolite or molecular sieve as well astheir analogs and used indiscriminately unless otherwise specified.

[0026] 1. Type of the Substrate

[0027] Examples of the substrate that can be employed in the presentinvention are as follows:

[0028] 1) materials containing hydroxyl groups on the surface, selectedfrom a group consisting of oxides or mixed oxides of metals andnon-metals such as silicon, aluminum, titanium, tin, indium, etc., whichcan be used alone or in a mixture, for example, quartz, mica, glass, ITOglass (glass deposited with indium oxide of tin), tin oxide (SnO₂), andother conductive glass, silica, porous silica, alumina, porous alumina,titanium dioxide, porous titanium dioxide, silicon wafer and the likes,

[0029] 2) metals capable of reacting with a thiol or amino group, suchas gold, platinum, silver, copper, and the like;

[0030] 3) polymers having various functional groups on their surfaces,such as PVC, a Merrifield peptide resin and the like;

[0031] 4) semiconductive materials, such as selenium-zinc (ZnSe),gallium-arsenic (GaAs) and indium-phosphor (InP), and the like;

[0032] 5) Natural materials of high molecular weight, which carryhydroxyl groups on their surfaces, such as cellulose, starch (e.g.,amylose and amylopectin), lignin and the like; or

[0033] 6) Natural or synthetic zeolite or molecular sieve analogs, asdefined in below.

[0034] 2. Type of Molecular Sieve

[0035] The molecular sieve, i.e., zeolite and its analogous molecularsieve that can be employed in the present invention are as follows:

[0036] 1) Natural and synthetic zeolite,

[0037] 2) Modified molecular sieve wherein all or a part of the siliconatoms in the zeolite skeleton are replaced with other atoms such asphosphorous (P) or the like (e.g., AlPO₄, SAPO, MeAPO, MeAPSO typemolecular sieve),

[0038] 3) Modified molecular sieve wherein all or a part of the siliconatoms in the zeolite skeleton are replaced with other atoms such asboron (B), gallium (Ga). Titanium (Ti), etc.,

[0039] 4) Molecular sieves by the combination of the above modificationsof the above modifications of item 2 and 3,

[0040] 5) Porous metals or silicon oxides (e.g., silicalite, MCM typeporous silica, porous titanium dioxide, niobium dioxide, etc.) or mixedoxide thereof, or

[0041] 6) Porous molecular sieves prepared with any other elements aloneor in a mixture.

[0042] 3. Type of Linking Compound

[0043] The linking compound in the present invention means the compoundhaving functional groups capable of chemically reacting with substratesor zeolite at each of the both terminals. The functional groups capableof chemically reacting with the substrate or zeolite means a groupcapable of chemically binding to hydroxyl group such as, for example,trichlorosilyl group (—SiCl₃), trimethoxysilyl group (—Si(CH₃)₃) oriscyanato group (—N═C═O) with respect to the substrate such as zeoliteor glass having surface hydroxyl groups, and thiol with respect tosubstrates such as gold. Those compounds carrying such functional groupshave been known to be capable of forming a self-assembled monolayer(SAM) when reacted with said substrate.

[0044] It is understood that a functional group capable of chemicallyreacting with a substrate can be determined depending on the nature(namely, the functionality) of the substrate's surface and can besuitably selected by a person having ordinary skill in the art.

[0045] The linking compounds that can be employed in the presentinvention can be preferably selected from the following compounds offormula 1 to 7 or a combination thereof: R₃Si-L-X (1) MR′₄ (2) Y-L-Y (3)R₃Si-L-Y (4) HS-L-X (5) HS-L-SiR₃ (6) HS-L-Y (7)

[0046] Wherein, R represents a halogen atom, C₁-C₄ alkoxy or alkylgroup; L represents a hydrocarbon residue, e.g., substituted orunsubstituted C₁-C₁₇ alkyl, aralkyl or aryl group, which may have atleast one heteroatom such as oxygen, nitrogen and sulfur; X represents aleaving group such as a halogen atom; provided that at least one of thethree Rs in a SiR₃ group denote a halogen or alkoxy group; R′ is thesame as R and the two of four R's in MR′₄ denote a halogen or alkoxygroup; M represents Si or a transition metal such as Ti or Zr; Yrepresents a ligand having a functional group selected from a groupconsisting of hydroxyl, thiol, amine, ammonium, sulfone and its salt,carboxyl acid and its salt, acid anhydride, epoxy, aldehyde, ester,acrylate, isocyanate (—NCO), sugar residue, double bond, triple bond,diene, diyne, alkylphosphine, alkylamine as well as a reactivefunctional group of various coordination compounds capable of exchangingtheir ligands; provided that said functional group can exist in themiddle or at the terminal ends of the ligands.

[0047] The linking compound combined to the substrate or zeolite canhave at least one functional group in the skeleton of the linkingcompound to give the secondary chemical bonding. To illustrate, when alinking compound combined to the substrate contains formyl group (—CHO)in the molecule and another linking compound combined to the surface ofzeolite has amino group (—NH₂) in the molecule, zeolite can combine tothe substrate via a chemical linkage of linking compound-linkingcompound since a chemical reaction between the amino group and theformyl group can easily happen.

[0048] As illustrated above, another linking compound or a bifunctionalcompound can intermediate in the linkage of linking compound-linkingcompound, for instance the following interposition compound can beexemplified: at least a compound selected from a group consisting offullerene (C₆₀, C₇₀), carbon nanotubes, α,ω-dialdehyde, dicarboxylicacid, dicarboxyl acid anhydride, amine-dendrimer, polyethylene imine,α,ω-diamine, a complex of [M(salan)] (wherein M represents Co, Ni, Cr,Mn, Fe and the like, and salan representsN,N-bis(salicylidene)ethylenediamine), and metal porphyrin derivatives.

[0049] Considering collectively the above matters, a linking compoundshould have at least two functional group, one for combining with thesubstrate and another one for chemically combining with the functionalgroup of the other linking compound bound to the surface of the otherzeolite or particles thereof. The matching or combination of the linkingcompound and its functional group can greatly vary and is easilyachieved by a person having ordinary skill in the pertinent artdepending on the necessity. Those variations and modifications are alsoincluded in the scope of the present invention if they employ theconcept of the present invention.

[0050] 4. Chemical Reaction of Linking Compounds with a Substrate orZeolite

[0051] Since substrates such as glass and molecular sieves such aszeolite have hydroxyl groups on their surface as described above, theycan react with linking compounds having a suitable functional groupcapable of reacting with hydroxyl group to form a composite ofsubstrate-linking compound or linking compound-zeolite. Further, sincesome functional group can be modified or changed to a new functionalgroup by a suitable treatment, a material having any adequatefunctionality on its surface can be modified through a chemicaltreatment so as to have new functionality. The reaction and itscondition for said treatment have been publicly known in this field.

[0052] Although metals such as gold does not have hydroxyl group on thesurface, it exhibit a superior reactivity to thiol group and so can beused as a substrate in the present invention owing to the remarkablereactivity to the linking compound introduced with one terminal thiolgroup. The compound having a one terminal thiol group can be used as alinking compound or blocking compound to the substrate of gold.

[0053] The substrate or zeolite particles are put into a containercontaining an organic solvent such as toluene, to which a linkingcompound is added and then the mixture is heated. Instead of toluene,another organic solvent such as hexane, benzene, tetrachlorocarbon,alcohol, etc. can be adequately used for the reaction. Upon thecompletion of reaction, the substrate is taken out and then washed withtoluene. When executing such a chemical bonding onto the surface ofzeolite, the vapor of the organic compound can be used sometimes toraise the chemical bonding directly. The zeolite in the dispersed liquidis filtered through filter paper. and washed well with the organicsolvent. When the zeolite particle is too small to use filter paper, acentrifuge is employed to separate the particles. The zeolite crystalsare introduced into a reaction container containing toluene and thendispersed well by an ultrasonic washer. Said compounds also can beevaporated without solvent under reduced pressure to vacuum so as tocombine with the substrate or zeolite.

[0054] 5. Method for Forming a Pattern on the Surface of Substrate

[0055] Although there are many methods for the formation of a pattern onthe substrate surface, the present invention employs the following threemethods. “Formation of a pattern” in the present invention means thatthe surface is blocked so that zeolite will react or will not react withthe surface in a selective manner. The present method is not restrictedon to the three methods, and any modifications or method that can givethe same effects with those methods fall within the scope of the presentinvention.

[0056] First, there is a method wherein a UV ray is employed to modifylinking compounds.

[0057] On a substrate to which linking compounds are combined, apattern-formed photomask is put and then UV ray (254 nm) is irradiatedfor a suitable time. In the region to which a UV ray has beenirradiated, said terminal functionality of the linking compounds thatare combined onto the substrate will be modified. In the region to whicha UV ray has not been irradiated, the terminal functionality of thelinking compounds that are combined onto the substrate will stillremain. Accordingly, a difference in the chemical functionality ariseson the surface of substrate along the shape of the pattern. The changeof the functionality by the irradiation of UV ray can be performedconversely.

[0058] Second, there is a method wherein blocking compounds or linkingcompounds are directly applied on the substrate in a microcontactingmanner.

[0059] In the present invention, the blocking compound means a compoundthat has only one functional group which will react with the substrate,and as a result, does not have any functional group which will reactwith zeolite or the other linking compound at the opposite end. Forexample, it includes trialkoxyalkylsilane (RSi(OR)₃, R=alkyl) ortrichloroalkylsilane (RSiCl₃, R=alkyl). In said blocking compound, alkylgroup preferably has at least six carbon atoms, more preferably at leastten carbon atoms.

[0060] On a PDMA (polydimethylsiloxane) stamp on which a pattern hasbeen formed, a solution of octadecyltrichlorosilane (OTS) in hexane isapplied, and then said stamp is mounted on a spin coater. The PDMS stampwas rotated to uniformly distribute octadecyltrichlorosilane thereon andthen impressed on a glass plate. The glass plate was left at roomtemperature for more than one hour and then dried at 120° C. for fiveminutes. Octadecyltrichlorosilane reacts with silanol group of the glassto form an octadecyl monolayer along the shape of the pattern. Namely,an octadecyl monolayer is formed in the region of the glass surface withwhich the stamp had contacted, while silanol remains unreacted in theregion of the glass surface with which the stamp has not contacted. Whenthe surface of the glass plate on which octadecyl groups are combined ina pattern is treated with a linking compound as described above, thearea wherein octadecyl groups are already combined will still remain asit is, while the linking compound is combined only to the region inwhich hydroxyl group (—OH) exists to give new functionality.Accordingly, the chemical functionality will be differentiated along theshape of the pattern.

[0061] Third, there is a method wherein a non-reactive metal isdeposited on a part of the surface to block the metal-deposited surface.In general, any metal that can be applied in conventional chemicaldeposition may be employed in the present invention. The presentinvention exemplifies a deposition of platinum, to which the scope ofthe invention is not restricted.

[0062] By using the procedure that is similar to the method using a UVray, a pattern-formed mask is put on the substrate and then platinum isdeposited in a thickness of about 15 nm by means of a vacuum thermaldepositing machine. The area contacted with the mask preserves thefunctionality of substrate without depositing platinum, while theexposed area is deposited with platinum to have the functionality ofplatinum. In this way, a pattern can be formed so that on the surface ofsubstrate has diverse chemical functionality different from each other.

[0063] The method for forming a pattern on the surface of substrate witha linking compound or blocking compound is not restricted to the abovemethods only.

[0064] 6. Method for Forming a Patterned Monolayer or Multilayer ofZeolite on the Surface of Substrate

[0065] When zeolite particles arc chemically combined with apattern-formed substrate having a difference in its chemicalfunctionality along the pattern, zeolite will combine along the patterndue to its functionality.

[0066] Meanwhile, zeolite particles may be physically attached on thepatterned zeolite monolayer of a composite during the preparationthereof. These zeolite particles physically attached thereon can beeasily removed by ultra-sonic washing.

[0067] A composite having a patterned zeolite multilayer can be producedeasily by repeating said methods as described above. Specifically, apatterned zeolite bilayer (double layer) will be formed by repeatedlytreating zeolite particles having a functional group capable ofchemically reacting with the functional group of the linking compoundwhich has already combined onto a patterned zeolite monolayer, and apatterned zeolite multiplayer will be formed by repeating the aboveprocedure for the bilayer.

[0068] In a multilayer composite, the types of zeolite consisting of theupper and lower layers are the same as or different from each other, andthe patterns of the upper and lower layers are the same as or differentfrom the other.

BRIEF DESCRIPTION OF THE DRAWING

[0069]FIGS. 1 and 2 are SEM (scanning electron microscope) photographsof a patterned zeolite ZSM-5 monolayer on a glass plate (magnification:×30), which were prepared by the method in Example 8 (using a blockingcompound).

[0070]FIGS. 3 and 4 are SEM (scanning electron microscope) photographsof a patterned zeolite ZSM-5 monolayer on a glass plate (magnification:×30 and ×100, respectively), which were prepared by the method inExample 4 (using a UV ray irradiation).

[0071] FIGS. 5 is a SEM (scanning electron microscope) photograph of apatterned zeolite ZSM-5 monolayer on a gold plate (magnification: ×100),which was prepared by the method in Example 6 (using a UV rayirradiation).

[0072]FIG. 6 is a SEM photograph of the ZSM-5 monolayer of zeolitepatterned on a glass plate (magnification: ×30), which was prepared bythe method in Example 10 (vacuum deposition of platinum).

[0073]FIGS. 7, 8 and 9 are SEM (scanning electron microscope)photographs of a patterned zeolite ZSM-5 monolayer on a glass plate(magnification : ×30, ×180 and ×800, respectively), which were preparedby the method in Examples 7 (using a UV ray irradiation) and 11 (using adeposition of platinum).

[0074]FIGS. 10 and 11 are SEM photographs of a patterned zeolite ZSM-5and zeolite A monolayer on a glass plate (magnification: ×5000,respectively), in which the zeolite monolayer is largely expanded.

[0075]FIGS. 12, 13 and 14 are SEM photographs of a patterned zeoliteZSM-5 double-layer on a glass plate (magnification: ×100, ×40000, and×60000, respectively), which were prepared by the method in Examples 13(using a UV ray irradiation).

[0076]FIGS. 15 and 16 are SEM photographs of a patterned zeolite ZSM-5multilayer on a glass plate (magnification: ×70000, respectively), whichshow the sectional view of the multilayer.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0077] The present invention will now be described in detail byfollowing specific but non-limiting embodiments. FIGS. 1 through 13attached are referenced together in this connection.

EXAMPLES Example 1 Pre-treatment of Substrate

[0078] A substrate such as glass, silicon wafers or the like was dippedin about 10% aqueous hydrochloric acid solution under heating for atleast an hour or in a mixed solution of ammonium persulfate ((NH₄)₂S₂O₈)and sulfuric acid for at least an hour. Then the substrate was washedwith distilled water, which was again dipped in an aqueous ammoniumsolution for fifteen minutes and further in acetic acid for about thirtyminutes. The resulting substrate was thoroughly washed with distilledwater and stored in distilled water. The substrate was taken out anddried, when used.

Example 2 Preparation of Gold Substrate

[0079] On a substrate such as glass, silicon wafer or the like, titan orchrome was first deposited by vacuum evaporation to a thickness of 100Å. On the layer of titan or chrome, gold was further deposited by vacuumevaporation to a thickness of 1000 Å. The resulting substrate was washedwith piranha solution prepared by mixing sulfuric acid and hydrogenperoxide in a ratio of 7:3. The substrate was heated at 300° C. undervacuum for three hours and cooled, before using.

Example 3 Preparation of a Patterned Monolayer of Zeolite through aChemical Ionic Bond on the Pattern Formed by UV Ray (λ=254 nm); IonicBond

[0080] A glass plate was dipped in 50 ml of hexane containing(3-cyanopropyl)trichlorosilane (Cl₃Si—(CH₂)₃—CN:0.05 ml) and left atroom temperature for 24 hours. The glass plate combined with3-cyanopropyl group was taken out and dipped in conc. HCl in a flask,which was heated at 95 to 100° C. for 2 hours. The cyano group waschanged to carboxyl group through hydrolysis. The glass plate combinedwith carboxyl group [glass-(CH₂)₃—CO₂H] was taken out and dipped in asaturated solution of sodium bicarbonate (NaHCO₃) for 12 hours. Thehydrogen ion was substituted with a sodium ion through neutralizationand the glass plate combined with the group of (CH₂)₃—CO₂ ⁻.Na⁺ could beobtained. The glass plate was dipped again in 1 M AgNO₃ solution for 12hours. Then the sodium ion was changed to a silver ion through ionexchange and the glass plate combined with the group of (CH₂)₃—CO₂ ⁻.Ag⁺was obtained.

[0081] On the glass plate combined with the group of (CH₂)₃—CO₂ ⁻.Ag⁺, aphotomask on which a pattern was formed was put and irradiated with UVray (λ=254 nm) for about 1 hour. The silver ion bound to the areaexposed to UV ray was reduced to silver and the area not exposed to UVray was left as it was. Accordingly the glass plate on which a patternof —(CH₂)₃—CO₂ ⁻.Ag⁺ group was formed was obtained.

[0082] The zeolite particles were introduced into a reaction vesselcontaining toluene and subsequently 3-aminopropylethoxysilane (APS) wasadded. The mixture was heated to react. After the completion of thereaction, the zeolite combined with 3-aminopropyl group was filtratedand washed thoroughly with toluene and ethanol. The zeolite combinedwith 3-aminopropyl group was added in 90% ethanol wherein sodiumbicarbonate and iodomethane (CH₃I) were dissolved and agitated at 60° C.for 24 hours. The zeolite particles combined with the group of—(CH₂)₃—N(CH₃)₃ ⁺.I⁻ were filtrated through a filter paper and thenwashed with ethanol and distilled water.

[0083] The zeolite particles combined with the group of —(CH₂)₃—N(CH₃)₃⁺.I⁻ were introduced into a reaction vessel containing ethanol to bedispersed well, in which the glass plate combined with the group of(CH₂)₃—CO₂ ⁻.Ag⁺ patterned was dipped. The temperature was elevated to60 to 78° C. and the glass plate was kept for 10 minutes andintermittently subjected to an ultrasonic vibration. The glass plate wastaken out and dipped in toluene in a bottle. Subsequently the glassplate was subjected to an ultrasonic vibration to remove any zeoliteparticles which were loosely attached on the monolayer. Thus thepatterned monolayer of zeolite could be prepared.

[0084] In said method for the preparation, the patterned monolayer ofzeolite can be prepared also using a gold plate instead of the glassplate. When the gold plate is employed, however, the one terminal of theorganic molecule combined to the gold plate should have a thiol group(—SH) instead of trichlorosilyl (—SiCl₃) or trialkoxysilyl (—Si(OR)₃;R=methyl or ethyl) group because the thiol group can combine only ontothe metal surface sturdily.

Example 4 Preparation of a Patterned Monolayer of Zeolite through aChemical Covalent Bond on the Pattern Formed by UV Ray (Mercury LightSource)

[0085] A glass plate was dipped in a reaction vessel containing toluene,to which (3-iodopropyl)trimethoxysilane was added. After being heatedfor 3 hours, the glass plate was washed well with toluene.

[0086] The glass plate combined with 3-iodopropyl group was undergonethrough the procedure of patterning by UV ray described in Example 3.Then there could be obtained a patterned glass plate wherein the iodogroup in the area exposed to UV ray was decomposed and 3-iodopropylgroup in the area not exposed was left as it was. Zeolite was introducedinto a reaction vessel containing toluene to be dispersed well, whereinthe glass plate combined with 3-iodopropyl group patterned was dipped.After being heated for 3 hours, the glass plate was taken out and dippedin toluene in a glass bottle. Subsequently the glass plate was subjectedto an ultrasonic vibration to remove any zeolite particles which wereloosely attached on the monolayer. Thus the patterned monolayer ofzeolite could be prepared.

Example 5 Preparation of a Patterned Monolayer of Zeolite through aChemical Covalent Bond on the Pattern Formed by UV Ray (Mercury LightSource)

[0087] A glass plate was dipped in a reaction vessel containing toluene,to which 1,4-diisocyanatobutane was added. The one of two isocyanategroups reacts with the glass plate to form the urethane bond and theother isocyanate group was left unreacted on the glass surface as itwas.

[0088] The glass plate combined with isocyanate group was undergonethrough the procedure of patterning by UV ray described in Example 3.Then there could be obtained a patterned glass plate wherein theurethane group in the area exposed to UV ray was decomposed andisocyanate group bound to urethane in the area not exposed was left asit was. Zeolite was introduced into a reaction vessel containing tolueneto be dispersed well, wherein the glass plate combined with isocyanategroup patterned was dipped. After being heated for 3 hours, the glassplate was taken out and dipped in toluene in a glass bottle.Subsequently the glass plate was subjected to an ultrasonic vibration toremove any zeolite particles which were loosely attached on themonolayer. Thus the patterned monolayer of zeolite could be prepared.

Example 6 Preparation of a Patterned Monolayer of Zeolite through aChemical Covalent Bond on the Pattern that was Formed by UV Ray (MercuryLight Source)

[0089] After a gold plate was dipped in 1 mM chloroform solution of1-mercapto-11,13-pentacosadiyonoic acid (HS(CH₂)₁₀C≡C—C≡C(CH₂)₁₁—COOH)for 24 hours, it was taken out and washed with chloroform. Undernitrogen atmosphere, the glass plate was undergone through the procedureof patterning by UV ray described in Example 3. Then the polymerizationwas raised at the monolayer combined to the area exposed to UV ray toform network between the molecular chains. The self-assembled monolayer(SEM) in the portion not exposed to UV ray was removed and then apatterned gold plate on which the organic substance was selectivelycombined could be obtained.

[0090] The method for removing the portion not exposed to UV ray can becarried out generally through the method for isolating thiol from thegold surface. For instance, the method of reducing electrochemically,the method through the heat treatment and the method employing acorrosive solvent can be exemplified.

[0091] As such, the methods for isolating thiol from the gold surfacehave been well known in the pertinent art.

[0092] The zeolite combined to 3-aminopropyl group prepared in Example 3was dispersed sufficiently in a suitable organic solvent (e.g., tolueneor dichloromethane) wherein a coupling agent such asdicyclohexylcarbodiimide (DDC) and a base catalyst such as4-dimethylaminopyridine (DMAP) were dissolved and subsequently the goldplate was dipped to be heated at 80° C. for 48 hours.

[0093] The gold plate was taken out and dipped in toluene in a glassbottle. Subsequently the glass plate was subjected to an ultrasonicvibration to remove any zeolite particles which were loosely attached onthe monolayer. Thus the patterned monolayer of zeolite could beprepared. The coupling agent can be replaced with the other couplingagents that have been generally used in the pertinent art.

[0094] Further, as the zeolite can be combined with the substratethrough the chemical reaction between the carboxyl group of substrateand the amino group of zeolite, the zeolite monolayer patterned on thegold plate can be prepared also by activating the carboxyl group ofsubstrate so as to react easily with the amino group. For example, thepatterned gold plate was dipped in dimethylformamide solution whereintrifluoroacetic anhydride ((CF₃CO)₂O) and triethylamine were dissolvedfor twenty minutes. The terminal on the gold plate, i.e., carboxyl acidwas changed to acetic acid trifluoroacetic anhydride (R—COOCOCF₃). Sucha transform indicates an activated state of carboxyl acid and makes itreact easily with amino group. The gold plate was taken out and washedwith an organic acid and then dipped in toluene wherein zeolite combinedwith 3-aminopropyl group was dispersed. The reaction was carried out atroom temperature for 48 hours. The gold plate was taken out and dippedin toluene in a glass bottle. Subsequently the glass plate was subjectedto an ultrasonic vibration to remove any zeolite particles which wereloosely attached on the monolayer. Thus the zeolite monolayer patternedon the gold plate could be prepared as described above.

Example 7 Preparation of a Patterned Monolayer of Zeolite through theDirect Growth of Zeolite Crystals on the Pattern that was Formed by UVRay (Mercury Light Source)

[0095] According to the procedure described in Examples 3 and 4, theglass plate combined respectively with 3-aminopropylmethyl, propyl,3-iodopropyl or 3-aminopropyl was prepared by using(3-aminopropyl)methyldiethoxysilane, propyltrimethoxysilane,(3-iodopropyl)trimethoxylsilane or (3-aminopropyl) triethoxysilane.

[0096] On the glass plate combined with an organic silane, a photomaskscored with the pattern was put and irradiated with UV ray. The time ofirradiation varies depending on the sort of organic silane and ispreferably ranged from 10 minutes to 1 hour. The decomposition wasraised in the area exposed to UV ray. Accordingly a glass plate whereinthe organic silane layer was patterned could be obtained. The patternedglass plate was put in the zeolite synthetic gel and zeolite was growndirectly on the glass plate. The direct growth of zeolite crystal wasoccurred in the area exposed to UV ray only. In this way, a patternedmonolayer of zeolite could be obtained by the selective growth ofcrystal on the glass plate. To illustrate, observing the preparatoryprocedure for, growing gel of ZCM-5 zeolite, tetrapropyl ammoniumhydroxide (TPAOH) as a zeolite template was dissolved in water andtetraethyl orthosilicate (TEOS) as a silicone source was added theretoand agitated till the uniform liquid was obtained. Subsequently sodiumaluminate as an aluminum source was added and agitated again till theuniform liquid was obtained. The final composition of zeolite was shownas SiO₂:Al₂O₃:TPAOH:Na₂O:H₂O=0.1-1:0-0.035:0.1:0-0.017:20-150. Theobtained synthetic gel and the patterned glass plate were put in anautoclave to be subject to the reaction at 120 to 180° C. for 3 to 12hours.

[0097] The glass plate was taken out and dipped in toluene in a glassbottle. Subsequently the glass plate was subjected to an ultrasonicvibration to remove any zeolite particles which were loosely attached onthe monolayer to be removed. Thus the patterned monolayer of zeolitecould be prepared.

[0098] The variously patterned monolayer of zeolite can be obtained bychanging the synthetic gel in the sort of zeolite. Producing thesynthetic gel of zeolite has been widely known in the pertinent art.

Example 8 Preparation of a Patterned Monolayer of Zeolite through aChemical Covalent Bond on the Pattern Formed by Chemicals

[0099]

[0100] The stamp on which a pattern was formed with polydimethylsiloxane(PDMS) was applied with the hexane solution of octadecyltrichlorosilane(OTS) and mounted on a spin coater. The PDMS stamp is rotated touniformly distribute octadecyltrichlorosilane and then impressed on aglass plate. The glass plate is left at room temperature for more thanone hour and is dried at 120° C. for five minutes.Octadecyltrichlorosilane reacts with silanol of glass to form anoctadecyl monolayer in accordance with the shape of pattern. Namely theoctadecyl monolayer is formed in the area wherein the stamp reached tothe glass surface, while silanol on the glass surface is left as it isin the area wherein the stamp did not reach to the glass surface.

[0101] The obtained glass plate whereon octadecyl group was patternedwas dipped in a reaction vessel containing toluene, wherein(3-chloropropyl)trimethoxysilane was added. After being heated for 3hours, the glass plate was washed with toluene to give a glass platewhereon octadecyl and 3-chloropropyl groups were patterned. The glassplate whereon octadecyl and 3-chloropropyl groups were patterned wasdipped in toluene wherein zeolite was dispersed and heated for 12 hours.The glass plate was taken out and dipped in toluene in a glass bottle.Subsequently the glass plate was subjected to an ultrasonic vibration toremove zeolite particles which are loosely attached on the monolayer.

Example 9 Preparation of a Patterned Monolayer of Zeolite through theDirect Growth of Zeolite Crystals on the Pattern that was Formed byChemicals

[0102] The glass plate on which the monolayer of octadecyl group waspatterned was prepared by using the stamp whereon a pattern was formedwith polydimethylsiloxane (PDMS) in accordance with the proceduredescribed in Example 8.

[0103] As described in Example 7, the glass plate patterned withoctadecyl group was put in a pressured reaction vessel containing gelfor synthesis and zeolite was subjected to the direct growth of crystalon the glass plate. The zeolite crystal formed to grow only in the areawhereto octadecyl group was not bound and a patterned monolayer ofzeolite was produced.

Example 10 Preparation of a Patterned Monolayer of Zeolite through aChemical Covalent Bond on the Pattern Formed by the Deposition ofPlatinum

[0104] The mask on which a pattern is formed was put on the glass and avacuum evaporation depositor deposited platinum to the thickness of 15nm. Platinum was not deposited in the area with which the mask wascontacted to prevent the treatment, but was deposited in the areaexposed. In this way, the glass plate on which platinum and3-chloropropyl group were patterned was obtained by treating the glassplate on which the pattern of platinum was formed in accordance with theprocedure described in Example 8 and also the zeolite monolayer wasproduced thereon.

Example 11 Preparation of a Patterned Monolayer of Zeolite through theDirect Growth of Zeolite Crystal on a Pattern that was Formed byDeposition of Platinum

[0105] A pattern of platinum was formed on a glass plate by thedeposition of platinum in the same manner as in Example 10. The glassplate was put into the gel for the synthesis of zeolite and subjected tothe crystal growth in the same manner as in Example 7. The crystalgrowth occurred only in the area on which a pattern of platinum was notformed.

Example 12 Preparation of a Patterned Bilayer of Zeolite through aChemical Ionic Bond on a Pattern that was Formed by UV Ray (MercuryLight Source)

[0106] Firstly, A glass plate on which a patterned monolayer of zeolitewas formed was prepared in the same manner as in Example 3.

[0107] Separately, zeolite combined with the group of (CH₂)₃—CO₂ ⁻.Na⁺was prepared and dispersed in toluene. The glass plate on which apatterned zeolite monolayer was formed was dipped in said solution., Thetemperature was elevated to 60˜78° C. and kept for 10 minutes, duringwhich the glass plate was vibrated by an ultrasonic washerintermittently. The glass plate was taken out and dipped in toluene in abottle. Subsequently the glass plate was subjected to an ultrasonicvibration to remove any unreacted zeolite particles which were looselyattached on the zeolite bilayer. Thus a patterned zeolite bilayer ofcould be prepared.

Example 13 Preparation of a Patterned Bilayer of Zeolite through aChemical Covalent Bond on the Pattern that was Formed by UV Ray (MercuryLight Source)

[0108] Firstly, a glass plate on which a patterned monolayer of zeolitewas formed was prepared in the same manner as in Example 4.

[0109] Separately zeolite combined with 3-iodopropyl group was thenprepared and dispersed in toluene, in which the glass plate on which apatterned monolayer of zeolite had been formed was dipped. The glassplate was heated for 3 hours and taken out and dipped in toluene in abottle. Subsequently the glass plate was subjected to an ultrasonicvibration to remove any unreacted zeolite particles which were looselyattached on the zeolite bilayer. Thus a patterned zeolite bilayer ofcould be prepared.

Example 14 Preparation of a Patterned Bilayer of Zeolite through aChemical Covalent Bond on the Pattern that was Formed by the Depositionof Platinum

[0110] Firstly, a glass plate on which a patterned zeolite monolayer wasformed was prepared in the same manner as in Example 9.

[0111] Separately zeolite combined with 3-iodopropyl group was preparedand dispersed in toluene, wherein the glass plate whereon a patternedmonolayer of zeolite was formed was dipped. The glass plate was heatedfor 3 hours and taken out and dipped in toluene in a bottle.Subsequently the glass plate was subjected to an ultrasonic vibration toremove any unreacted zeolite particles which were loosely attached onthe zeolite bilayer. Thus a patterned zeolite bilayer of could beprepared.

Example 15 Preparation of a Patterned Multilayer of Zeolite

[0112] First, a glass plate on which a patterned bilayer of zeolite wasformed was prepared in the same manner as in Example 12.

[0113] Then, zeolite combined with the group of (CH₂)₃—N(CH₃)₃ ⁺.I⁻ wasdispersed in ethanol in a reaction vessel and dispersed thoroughly,during which the glass plate was intermittently vibrated by anultrasonic washer. The glass plate was taken out and dipped in toluenein a bottle. Subsequently the glass plate was subjected to an ultrasonicvibration to remove any unreacted zeolite particles which were looselyattached on the zeolite bilayer. Thus a patterned zeolite tri-layer ofcould be prepared.

[0114] By repeating the procedure, the number of layers in themultilayer can be controlled in accordance with the number of repeatingtimes. Further repeating the procedure in the same manner as in Examples13 and 14 could produce the zeolite multilayer.

Example 16 Preparation of a Patterned Monolayer of Zeolite Composite onthe Pattern that was Formed by UV Ray (Mercury Light Source)

[0115] In this Example, a glass plate on which a patterned monolayer ofzeolite is formed was prepared in the same manner as in Example 7.

[0116] The glass plate was calcined and the organic substance existed inthe area wherein zeolite did not grow (or combine) was removed. Theglass plate was again put into the gel for the synthesis of zeolite andsubjected to the second crystal growth on the surface of glass.Primarily when a pattern of zeolite is obtained by the crystal growth ofZSM-5 zeolite, secondarily a pattern of zeolite composite is obtained bythe crystal growth of zeolite-A. The crystal growth can be progresseddifferently because of the difference of the growing speed between thesurfaces of glass and zeolite.

[0117] The combination of zeolite style other then said one could beemployed also.

Example 16 Analysis of Scanning Electron Microscope (SEM)

[0118] On a monolayer or multilayer of zeolite prepared in the samemanner as in said examples, the coating of platinum/palladium wasexecuted in a thickness of about 15 nm and an image of SEM was obtainedby a scanning electron microscope (model; Hitachi S-4300). FIGS. 1 to 16show the representative images of the SEM images of the variouscomposites prepared by the method of each example.

INDUSTRIAL APPLICABILITY

[0119] According to the present invention, a composite having apatterned zeolite monolayer or multilayer via a chemical bond can beprepared. In addition, the terminal functional group of the linkingcompound can be very diversely modified, and thus the bonding methodsalso can be very diversely modified. In addition, since it is possibleto control and modify the type and kind of zeolite as well as thepattern style of each layer in a multiple layer, the present inventionis very advantageous in view of practical use.

[0120] The composite having a patterned monolayer or multilayer ofmolecular sieve prepared according to the present invention can beusefully employed for a separating membrane for gas or liquid, a linearor nonlinear optical device, the optoelectronics, a membrane, a membranecatalyst, a sensor carrier, a photocell, or in the field of filmformation using the second growth of zeolite. In addition, it isexpected that there may be caused new physical property when zeoliteparticles form a pattern. Accordingly, such a new composite is expectedas an epoch-making material at the aspect of science as well as utility.

What is claimed is:
 1. A method for the preparation of azeolite-substrate composite comprising a patterned zeolite monolayer ormultilayer, characterized in that it comprises (i) combining a linkingcompound onto the surface of substrate, (ii) modifying the linkingcompound combined to the substrate or the functional group thereof byirradiating UV ray through a photomask having a pattern, (iii)selectively forming a zeolite layer on the area to which UV ray is or isnot irradiated, and (iv) optionally performing a calcination.
 2. Amethod for the preparation of a zeolite-substrate composite comprising apatterned zeolite monolayer or multilayer, characterized in that itcomprises (i) combining a linking compound to a part of the surface ofthe substrate so as to have a predetermined pattern and then combining ablocking compound to the remaining surface of the substrate, orcombining a blocking compound to a part of the surface of the substrateso as to have a predetermined pattern and then combining a linkingcompound to the remaining surface of the substrate, (ii) forming azeolite layer on the area to which the linking compound is combined, and(iii) optionally performing a calcination.
 3. A method for thepreparation of a zeolite-substrate composite comprising a patternedzeolite monolayer or multilayer, characterized in that it comprises (i)depositing a metal such as platinum onto a part of the substrate surfaceto form a metal layer so as to have a predetermined pattern. (ii)forming a zeolite layer by growing crystal or combining zeolite-linkingcompound on the remaining area, and (iii) optionally performing acalcination.
 4. The method as claimed in claim 1, characterized in thatsaid zeolite layer is formed after removing the portion to which UV rayis irradiated or the portion to which UV ray is not irradiated.
 5. Themethod as claimed in claim 2, characterized in that said linkingcompound having functional group at both terminals or a blockingcompound which does not have any functional group at the one terminalsuch as octadecyltrichlorosilane was applied and then bonded on a partof the substrate surface by the stamp method
 6. The method as claimed inany one of claims 1 to 5, characterized in that the patterned ornon-patterned layer of zeolite was previously formed on all or a part ofthe substrate surface.
 7. The method as claimed in any one of claims 1to 5, characterized in that said substrate is selected from the groupconsisting of: 1) all substances containing hydroxyl groups on thesurface, 2) metals capable of reacting with a thiol or amino group, 3)polymers having various functional groups on their surfaces, 4)semiconductive materials, 5) natural or synthetic zeolite or molecularsieve analogs,
 8. The method as claimed in any one of claims 1 to 5,characterized in that the linking compounds which form thesubstrate-linking compound and the zeolite (or its analog)-linkingcompound are identical or different from each other and selected fromthe compounds of the following formula 1 to 7 or a combination thereof.R₃Si-L-X (1) MR′₄ (2) Y-L-Y (3) R₃Si-L-Y (4) HS-L-X (5) HS-L-SiR₃ (6)HS-L-Y (7)

Wherein, R represents a halogen atom, C₁-C₄ alkoxy or alkyl group; Lrepresents a hydrocarbon residue, e.g., substituted or unsubstitutedC₁-Cl₇ alkyl, aralkyl or aryl group, which may have at least oneheteroatom such as oxygen, nitrogen and sulfur; X represents a leavinggroup such as a halogen atom; provided that at least one of the three Rsin a SiR₃ group denote a halogen or alkoxy group; R′ is the same as Rand the two of four R's in MR′₄ denote a halogen or alkoxy group; Mrepresents Si or a transition metal such as Ti or Zr; Y represents aligand having a functional group selected from a group consisting ofhydroxyl, thiol, amine, ammonium, sulfone and its salt, carboxyl acidand its salt, acid anhydride, epoxy, aldehyde, ester, acrylate,isocyanate (—NCO), sugar residue, double bond, triple bond, diene,diyne, alkylphosphine, alkylamine as well as a reactive functional groupof various coordination compounds capable of exchanging their ligands;provided that said functional group can exist in the middle or at theterminal ends of the ligands.
 9. The method as claimed in any one ofclaims 1 to 5, characterized in that zeolite is selected from the groupconsisting of: 1) Natural and synthetic zeolite, 2) Modified molecularsieve wherein all or a part of the silicon atoms in the zeolite skeletonare replaced with other atoms such as phosphorous (P) or the like (e.g.,AlPO₄, SAPO, MeAPO, MeAPSO type molecular sieve), 3) Modified molecularsieve in which all or a part of the aluminum atoms in the zeoliteskeleton are replaced with other atoms such as boron (B), gallium (Ga).Titanium (Ti), etc., 4) Molecular sieves by the combination of the abovemodifications of the above modifications of item 2 and 3, 5) Porousmetals or silicon oxides (e.g., silicalite, MCM type porous silica,porous titanium dioxide, niobium dioxide, etc.) or mixed oxide thereof,or 6) Porous molecular sieves prepared with any other elements alone orin a mixture.
 10. The method as claimed in claim 9, characterized inthat said linking compound can be intermediated by at least a compoundselected from a group consisting of fullerene (C₆₀, C₇₀), carbonnanotubes, α,ω-dialdehyde, dicarboxylic acid, dicarboxyl acid anhydride,amine-dendrimer, polyethylene imine, α,ω-diamine, a complex of[M(salan)] (wherein M represents Co, Ni, Cr, Mn, Fe and the like, andsalan represents N,N-bis(salicylidene)ethylenediamine), and metalporphyrin derivatives.
 11. The method as claimed in any one of claims 1to 5, characterized in that said zeolite layer is formed or originatedfrom zeolite (or analogous molecular sieve), zeolite (or analogousmolecular sieve)-linking compound or crystal grown zeolite.
 12. Themethod as claimed in any one of claims 1 to 5, characterized in that, ona patterned zeolite layer, an upper layer consisting of the same ordifferent kind of zeolite is formed so as to have a pattern.
 13. Themethod as claimed in claim 12, characterized in that the upper layer isformed so as to have a pattern the same or different from that of thelower layer.
 14. A composite of zeolite-substrate comprising a patternedlayer of zeolite prepared according to any one of claims 1 to
 5. 15. Acomposite of zeolite-substrate as claimed in claim 14, characterized inthat it comprises a plural of zeolite layers, of which type are the sameor different from each other.